WO1996038058A1 - Composition containing readily absorbable calcium and process for producing the same - Google Patents

Composition containing readily absorbable calcium and process for producing the same Download PDF

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Publication number
WO1996038058A1
WO1996038058A1 PCT/JP1996/000938 JP9600938W WO9638058A1 WO 1996038058 A1 WO1996038058 A1 WO 1996038058A1 JP 9600938 W JP9600938 W JP 9600938W WO 9638058 A1 WO9638058 A1 WO 9638058A1
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WIPO (PCT)
Prior art keywords
calcium
chondroitin sulfate
salt
acid
calcium salt
Prior art date
Application number
PCT/JP1996/000938
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French (fr)
Japanese (ja)
Inventor
Shinya Katsukura
Original Assignee
Nishimura, Masahiko
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nishimura, Masahiko filed Critical Nishimura, Masahiko
Priority to US08/952,738 priority Critical patent/US6203827B1/en
Priority to AU51625/96A priority patent/AU5162596A/en
Priority to DE69628754T priority patent/DE69628754T2/en
Priority to EP96908353A priority patent/EP0839459B1/en
Publication of WO1996038058A1 publication Critical patent/WO1996038058A1/en

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    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/70—Carbohydrates; Sugars; Derivatives thereof
    • A61K31/715—Polysaccharides, i.e. having more than five saccharide radicals attached to each other by glycosidic linkages; Derivatives thereof, e.g. ethers, esters
    • A61K31/737—Sulfated polysaccharides, e.g. chondroitin sulfate, dermatan sulfate
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/16—Inorganic salts, minerals or trace elements
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
    • A61K33/06—Aluminium, calcium or magnesium; Compounds thereof, e.g. clay
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
    • A61K33/06—Aluminium, calcium or magnesium; Compounds thereof, e.g. clay
    • A61K33/10—Carbonates; Bicarbonates
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs

Definitions

  • the present invention relates to a composition containing easily absorbable rubber and a method for producing the same.
  • Calcium is a component of bones and teeth, as well as a regulator of muscle, nervous system, and hormonal secretion.It is important for maintaining biological functions, and is involved in immune function. This has also been clarified. Insufficient calcium intake is known to be involved in the development of adult diseases such as hypertension, ischemic heart disease, and endocrine diseases, in addition to bone disease. Despite the growing interest in ecosystems, their intake is not always sufficient in our diet. For this reason, various calcium preparations and health foods containing calcium have been proposed and put on the market to make up for the shortage.
  • calcium compounds obtained by chemical synthesis calcium compounds derived from shellfish, shellfish, eggshell, animal bones, and plants derived from seaweeds
  • these calciums are not so highly absorbed into the body and are often used as preparations.
  • the present inventors have obtained a calcium preparation or a food additive containing calcium, which has good absorption into the body and good taste and flavor when ingested. Focusing on the fact that calcium is obtained from natural animal raw materials with a stable supply source, the results of experiments and research have shown that an outer shell consisting of two spines and a shell is obtained. Replacement paper with calcium compound obtained by firing (Rule 26) Found that it satisfies all the objectives, and also contains, as a main component, its practical production method and the resulting potassium compounds derived from it. Research and development were proceeded on the composition of the composition.
  • the present inventor added an appropriate amount of chondroitin sulfate belonging to the sulfhomcopolysaccharide to the calciumi conjugate obtained in this manner. It was discovered that the amount of calcium absorbed into the living body was significantly increased due to this phenomenon, and the result was reported in Japanese Patent Application No. 6-26096. Filed. As a result of further research and development, the absorption of calcium into the living body by the addition of chondroitin sulfate was confirmed by the above-mentioned In addition to the cases described above, the authors also wrote about the case of other animal calcium or general potassium salts such as synthetic lactate and carbonate lactate. Was found to be promoted. As described above, the absorption of calcium into the living body is promoted by the combined use with chondroitin sulfate, but the absorption is reduced by chondroitin. It was also found that there was a specific dependence on the concentration of sulfuric acid.
  • the chondroitin sulfate thus remarkably promotes the absorption of calcium into the living body, thereby increasing the concentration of calcium in the blood. There is no danger of sudden loss of power balance. Disclosure of the invention
  • the invention of the present application has been completed based on the above findings of the present inventors, and the features of the first invention are a calcium salt and a calcium salt of the calcium salt.
  • Food composition containing easily absorbable rubium characterized in that it contains chondroitin sulfate in the range of 0.2 to 5% by weight based on the amount of shim. In the thing.
  • the ratio of chondroitin sulfate to the calcium content is more preferably 0.3 to 2.5% by weight.
  • More specific replacement paper in which the present invention is applied to use of a natural calcium source (Rule 26)
  • the features of the second invention are as follows: (a) a calcium salt of carboxylic acid obtained by treating the outer shell and a calcium component of the calcium salt;
  • a food composition containing easily absorbable calcium characterized in that it contains chondroitin sulfate in the range of 0.2 to 5% by weight.
  • the feature of the third invention according to the present application is that the outer shell is calcined and hydrated to obtain hydroxyl hydroxide, which is then converted to organic. By reacting with and neutralizing calcium carbonate, the organic calcium carbonate is converted into a calcium salt, and the calcium salt of the calcium salt is reacted with the calcium salt of the calcium salt. Adding a chondroitin sulfate in the range of 0.2 to 5% by weight to produce a food composition containing a readily absorbable ruminium. It is in
  • the food composition containing the easily absorbable potassium salt of the present invention contains 0.2 to 5% by weight of a chondrolyte based on the calcium content of the potassium salt.
  • the inclusion of tin sulfate significantly accelerates the uptake of calcium into the body.
  • Chondroitin sulfate, along with heparin, keratosulfate, hyaluronosulfate, etc. belongs to the sulfhomcopolysaccharides that exist widely in the animal kingdom, especially Roitin sulfate and its salts have already been proven safe as food additives (emulsifiers, fish odor removers).
  • Chondroitin sulfate has D-gluconic acid in the chondrosamine derivative; and e-sulfuric acid in the repeating conjugate of disaccharide linked to glycoside. It is a water-soluble polymer having a molecular weight of about 500,000, and its aqueous solution exhibits viscous properties.
  • chondroitin sulfate is obtained from shark cartilage and the like. Obtained as the c isomer.
  • chondroitin sulfate As the blending amount of chondroitin sulfate with respect to the above-mentioned calcium salt, an extremely small amount of, for example, 0.01% by weight based on the calcium content is added. , The absorption of calcium is already improved, but at about 6% by weight, the absorption is significantly reduced. The effect of chondroitin sulfate is remarkable from about 0.2% by weight with respect to the calcium content, and particularly from about 0.3 to 2.5% by weight. Shows excellent absorption. On the other hand, if it exceeds 1%, the above effect tends to decrease gradually, and particularly if it exceeds 5%, the effect of promoting absorption of calcium is remarkably reduced.
  • a control range of about 0.2 to 5% by weight, preferably 0.3 to 2.5% by weight, based on the calcium content is used. Tin sulfate is added.
  • calcium is preferably used as a form of an inorganic salt such as a carbonate or an organic carbonate from the viewpoint of safety during incorporation into a living body.
  • a calcium source synthetic calcium lactate, calcium citrate, calcium carbonate and the like can be used.
  • the natural calcium sources particularly, calcium obtained by calcining a duck shell is preferable.
  • the second class accumulates crystals of carbonated calcium in its body wall and combines them as calcareous plates to form an outer shell.
  • the ovary is mainly harvested for its ovary, and is used for food. And causing problems.
  • most of the husk is made up of calcium and other relatively large amounts of magnesium, power rim, sodium, phosphorus, zinc, etc. It is a well-balanced calcium source containing trace mineral components. Replacement form from the point of view of industrial use (Rule 26) As mentioned above, it is economically easy to obtain as a large amount of fishery waste
  • the dinosaur used in the present invention belongs to the phylum Echinoderm and the dinosaur, and is used for edible purposes, for example.
  • Ezono ⁇ ? Representatives of Hampini, Pseudocarpaceae, and Pseudocarpaceae are representatives, but in recent years from overseas such as North America and South Korea. In addition, various types are imported in large quantities.
  • the outer shell obtained by collecting ovaries and the like as a raw material is first washed with water and dried appropriately. Next, it is placed in a normal heat-resistant heating furnace and heated. In this case, the carbonated rubber in the shell becomes calcium oxide when heated at about 95 ° C to 115 ° C, and the structure of the furnace body is reduced. However, by heating at the above-mentioned temperature for about 1 hour, the raw material is almost converted into calcium oxide, and the firing operation is completed.
  • the acids used for neutralization are commonly used in the food field in terms of safety when taken, solubility, absorption of calcium into the body, and taste and flavor.
  • Organic carboxylic acids are used, and depending on the application, L-lactate, carboxylic acid, linoleic acid, succinic acid, gluconic acid, acetic acid and acetic acid Binic acid or the like is used.
  • Replacement form (Rule 26) The formulation in the form of an aqueous solution thus obtained is then made into a powdery or granular form by a spreader, and a powdery form depending on the application. It is used as a tablet-like product or as an aqueous solution as a linking agent.
  • excipients such as sugar alcohols, particularly reduced maltose and perisitol to facilitate the granulation process.
  • Chondroitin sulfate is added to the calcium blend of this form at a ratio in the above range with respect to calcium.
  • the hull calcium which is preferably used in the present invention, calcium oxide obtained by calcining a dini outer shell at a high temperature is used to temporarily obtain calcium hydroxide. Therefore, the subsequent treatment such as a neutralization reaction is facilitated.
  • the organic acid is in the form of a calcium salt by the neutralization reaction with the organic carboxylic acid, the calcium can be safely and highly absorbed into the body. Can be ingested at
  • the type of the organic acid may be appropriately selected in consideration of the solubility and the like depending on the application in addition to the above-mentioned safety and absorbability.
  • the husk calcium is a single product, it is in vivo compared with other chemically synthesized carbonate calcium, egg shell calcium, and shell-derived calcium. Absorbency to water is remarkably high.
  • the magnesium content is specifically high (about 2%). It is known that this magnesium is generally a substance that participates in the process of absorbing potassium into a living body.
  • trace components such as sodium, potassium, zeolite, phosphorus, iron, zinc, etc. are well-balanced, and these components are also well-balanced. It is thought that it contributes to the absorption of the urine into the body.
  • heavy metals such as Hg, Cd, Pb, and As are less than about lppm or are not detected at all.
  • FIG. 1 shows the ratio of chondroitin sulfate to calcium in the compositions containing various calcium salts obtained according to the examples of the present invention.
  • FIG. 2 is a graph showing the absorption intestinal absorption (%) of calcium in the case of 0.6%) along with the passage (min) of circulation time (Circulation Time).
  • FIG. 2 shows the rat intestinal absorption (%) of calcium when lactate derived from husks obtained in Example 1 was administered.
  • FIG. 4 is a diagram showing the time course (min) of the case where the concentration of Georgiain sulfate was changed in the range of 0.15 to 6% by weight.
  • the outer shell After collecting the ovary of the puffer, the outer shell is washed with water and air-dried, and calcined in a firing furnace at a temperature of about 110 ° C for 1 hour to obtain calcium oxide. After being converted to water, it was sufficiently hydrated and converted to calcium hydroxide. 100 g of calcium hydroxide obtained in this manner was dissolved in 10 liters of water, and about 50% of 50% L-lactic acid was dissolved. Was added and the mixture was reacted at a temperature of 75 ° C. for 15 minutes to produce calcium coconut lactate.
  • lactate-derived calcium lactate obtained in the production process of Example 1 and the calcium lactate and canolecum carbonate obtained by the synthesis were the same as those in Example.
  • Compositions were prepared in proportions, but without the addition of chondroitin sulfate.
  • the abscissa indicates the progress of the circulation time (CirculationTime) (min), and the ordinate indicates the intestinal absorption rate of calcium (ABS) (%).
  • composition obtained by replacing lactic acid in Example 1 with succinic acid also showed almost the same calcium absorption as the composition containing UCAL *.
  • potassium carbonate absorption of the calcium carbonate composition obtained by processing the eggshell by the usual method was about 15 compared to the composition containing UCAL *.
  • the ratio of chondroitin sulfate (100%) to calcium is 0.6 to 6% by weight (20% of chondroitin sulfate to calcium lactate) Of the test compound UCAL * in Example 1 described above in which the concentration was changed to a concentration of 0.5 to 5% by weight (0.5 to 5% by weight). Um absorption tests were performed. In order to confirm the lower limit of the amount of chondroitin sulfuric acid, a similar experiment was performed with the proportions of calcium to 0.15% and 0.3% by weight, respectively. Was performed. The results are shown in Table 2 and FIG. In Fig. 2, the vertical axis of the graph shows the calcium absorption rate (%) and the horizontal axis shows the circulation time (min).
  • the ratio of chondroitin sulfate to calcium was in the range of 0.2 to 5.0% by weight, particularly in the range of 0.3 to 2.5% by weight.
  • the absorption rate gradually decreases as the concentration of chondroitin sulfate increases from 2% by weight to 5% by weight.
  • the value becomes the maximum absorption concentration.
  • the value was reduced to about 12 compared to the case of 1% of the value.
  • chondroitin sulfate shows a sufficient C absorptivity even at a concentration of about 0.3% by weight, but at 0.15% by weight, the value drops sharply. It is considered that about 2% by weight is a practical lower limit of the concentration of chondroitin sulfate to calcium.
  • the acute toxicity of bivalve calcium used as one of the starting materials of the compositions of the examples of the present invention was determined by a rat LD50 test. ⁇ Prepare a 0.5% solution of calcium (Ca (OH) 2O) in a coconut shell at pH 5.0 with 50% L-lactic acid (U-grade), and use it for 7 weeks (2 weeks). Oral (1000-500 mg / kg) and intravenous (100-29 Omg / kg) to rats (SD male) weighing ) And observed over a period of 14 days to determine the LD50 value.
  • the composition containing coconut shell calcium in the present invention is extremely safe as a pharmaceutical preparation or a food additive, etc. (Rule 26) It is considered to be fully usable. Industrial applicability
  • the composition into the body at the time of their ingestion can be obtained.
  • the absorption of calcium is significantly enhanced. Particularly, it is of little value as a fishery waste at present.
  • the calcium component of the husks is extremely good in the body.
  • a shim is obtained, and the composition obtained by blending it is used as a calcium preparation, as well as various foods and food additives that are excellent in taste and flavor. Having.

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Abstract

A composition containing readily absorbable calcium which comprises a calcium salt and 0.2 to 5 % by weight, based on the calcium contained in the calcium salt, of chondroitin sulfate. A calcium salt preferably used in this composition can be obtained by, for example, baking the external skeleton of sea urchin in an oven to thereby give calcium oxide, hydrating it into calcium hydroxide and then reacting it with an organic carboxylic acid to thereby give a calcium salt. The absorption of calcium in vivo is highly promoted by adding chondroitin sulfate. The calcium may be any one origninating in various natural and synthetic sources.

Description

明 細 書 易吸収性カ ル シ ウ ムを含有する組成物およ びそ の製造方法 技術分野  Description Composition containing easily absorbable calcium and method for producing the same
本発明は易吸収性力 ル シ ゥ ム を含有す る組成物およ びそ の製造 方法に関する 。 背景技術  TECHNICAL FIELD The present invention relates to a composition containing easily absorbable rubber and a method for producing the same. Background art
カ ル シ ウ ム は骨や歯の構成成分であ る と共に筋肉、 神経系、 ホ ル モ ン分泌の調節因子 と して生体機能の保持に重要であ り 、 ま た 免疫機能に関与す る こ と も 明 ら かに されてい る。 カ ル シ ウ ム の摂 取の不足は骨疾患の他、 高血圧、 虚血性心疾患お よび内分泌疾患 等の成人病の発現に関与す る こ とが知ら れてお り 、 一般に カ ル シ ゥ ム への関心が高ま り つ 、 あ る が、 我国の食生活において はそ の 摂取量は必ず し も充分ではない。 こ のためそ の不足を補 う ために 種々 の カ ル シ ウ ム製剤やカ ル シ ウ ム を含む健康食品が提案 さ れ市 版さ れてい る 。  Calcium is a component of bones and teeth, as well as a regulator of muscle, nervous system, and hormonal secretion.It is important for maintaining biological functions, and is involved in immune function. This has also been clarified. Insufficient calcium intake is known to be involved in the development of adult diseases such as hypertension, ischemic heart disease, and endocrine diseases, in addition to bone disease. Despite the growing interest in ecosystems, their intake is not always sufficient in our diet. For this reason, various calcium preparations and health foods containing calcium have been proposed and put on the market to make up for the shortage.
従来、 た と えば化学的合成に よ る カ ル シ ウ ム化合物、 貝や甲殻 類、 卵殻、 動物の骨に 由来する カ ル シ ウ ム化合物およ び海藻類か らの植物由来のカ ル シ ウ ム等が利用 されて い るが、 こ れ ら の カ ル シ ゥ ム は体内への吸収性がそれほ ど高 く な く 、 ま た多 く の場合製 剤と してあ る いは食品添加物と して用い る際の味や風味に問題が あ る ため に広 く 一般ィ匕さ れる に は到 っ て いない。  Conventionally, for example, calcium compounds obtained by chemical synthesis, calcium compounds derived from shellfish, shellfish, eggshell, animal bones, and plants derived from seaweeds Although calcium and the like are used, these calciums are not so highly absorbed into the body and are often used as preparations. Has not been widely used because of problems in taste and flavor when used as a food additive.
本発明者等は体内への吸収が良好でかつ摂取 し た際の味や風味 が良好な カ ル シ ウ ム製剤又はカゝ 、 る カ ル シ ウ ムを含有する食品添 加物を得る こ と のでき る カ ル シ ウ ム を供給源の安定 した天然の動 物性原料か ら得る こ と に着目 し 、 実験、 研究の結果、 ゥ 二 の棘お よび殻か ら な る外殻体を焼成 し て得 られる カ ル シ ウ ム化合物がか 差替 え 用紙 （規則 26) ゝ る 目的を満足す る こ と を発見 し、 さ ら にそ の実際的な製造方法 およ びそれに よ つ て得 られる ゥ 二由来の カ ル シ ゥ ム化合物を主成 分と して含む組成物の配合につ いて研究およ び開発を進めた。 The present inventors have obtained a calcium preparation or a food additive containing calcium, which has good absorption into the body and good taste and flavor when ingested. Focusing on the fact that calcium is obtained from natural animal raw materials with a stable supply source, the results of experiments and research have shown that an outer shell consisting of two spines and a shell is obtained. Replacement paper with calcium compound obtained by firing (Rule 26) Found that it satisfies all the objectives, and also contains, as a main component, its practical production method and the resulting potassium compounds derived from it. Research and development were proceeded on the composition of the composition.
こ の過程において本発明者は こ のよ う に して得たカ ル シ ウ ムィ匕 合物に対 して ス ル ホ ム コ多糖類に属する コ ン ド ロ イ チ ン硫酸を適 量配合す る こ と に よ っ て生体内へのカ ル シ ウ ム吸収量が著 し く 増 大す る こ と を発見 しそ の成果を特願平 6 — 2 6 0 9 9 6 号 と して 出願 した。 さ ら に引 き続 く 研究およ び開発の結果、 コ ン ド ロ イ チ ン硫酸の添加によ る カ ル シ ウ ム の生体内への吸収が前記ゥ ニ殻力 ル シ ゥ ム の場合のみな らず他の動物性カ ル シ ウ ム また は合成に よ る乳酸力 ル シ ゥ ム や炭酸力 ル シ ゥ ム等の一般の力 ル シ ゥ ム塩の場 合について も著 し く 促進さ れる こ と が発見さ れた。 ま た前記のよ う に カ ル シ ウ ム の生体内への吸収は コ ン ド ロ イ チ ン硫酸と の併用 によ っ て促進 さ れるが、 そ の吸収は コ ン ド ロ イ チ ン硫酸の濃度に ついて特異な依存性があ る こ と も発見さ れた。  In this process, the present inventor added an appropriate amount of chondroitin sulfate belonging to the sulfhomcopolysaccharide to the calciumi conjugate obtained in this manner. It was discovered that the amount of calcium absorbed into the living body was significantly increased due to this phenomenon, and the result was reported in Japanese Patent Application No. 6-26096. Filed. As a result of further research and development, the absorption of calcium into the living body by the addition of chondroitin sulfate was confirmed by the above-mentioned In addition to the cases described above, the authors also wrote about the case of other animal calcium or general potassium salts such as synthetic lactate and carbonate lactate. Was found to be promoted. As described above, the absorption of calcium into the living body is promoted by the combined use with chondroitin sulfate, but the absorption is reduced by chondroitin. It was also found that there was a specific dependence on the concentration of sulfuric acid.
前記コ ン ド ロ イ チ ン硫酸は こ の よ う に カ ル シ ウ ム の生体内への 吸収を著 し く 促進させ るが、 そ れに よ つ て血液中のカ ル シ ウ ム濃 度が急激に增大 して力 ル シ ゥ ム バラ ン ス が失われる おそれは全 く ない。 発明の開示  The chondroitin sulfate thus remarkably promotes the absorption of calcium into the living body, thereby increasing the concentration of calcium in the blood. There is no danger of sudden loss of power balance. Disclosure of the invention
本願発明は本発明者等の前記知見に基いて完成 された も の であ り 、 そ の第一の発明の特色はカ ル シ ウ ム塩およ び前記カ ル シ ウ ム 塩の カ ル シ ウ ム分に対 して 0 . 2 な い し 5 重量％の範囲の コ ン ド ロ イ チ ン硫酸を含む こ と を特徴 とす る易吸収性力 ル シ ゥ ム を含有 する 食品組成物にあ る 。  The invention of the present application has been completed based on the above findings of the present inventors, and the features of the first invention are a calcium salt and a calcium salt of the calcium salt. Food composition containing easily absorbable rubium, characterized in that it contains chondroitin sulfate in the range of 0.2 to 5% by weight based on the amount of shim. In the thing.
前記コ ン ド ロ イ チ ン硫酸のカ ル シ ウ ム分に対す る割合は よ り 好 ま し く は 0 . 3 ない し 2 . 5 重量％であ る。  The ratio of chondroitin sulfate to the calcium content is more preferably 0.3 to 2.5% by weight.
本願発明を天然カ ル シ ウ ム源の利用に適用 した よ り 具体的な第 差替 え 用紙 （規則 26) 二の発明の特色は ゥ 二 の外殻体を処理 し て得 られ る有 a カ ル ボ ン 酸の カ ル シ ウ ム塩と 、 こ の カ ル シ ウ ム塩のカ ル シ ウ ム分に対 してMore specific replacement paper in which the present invention is applied to use of a natural calcium source (Rule 26) The features of the second invention are as follows: (a) a calcium salt of carboxylic acid obtained by treating the outer shell and a calcium component of the calcium salt; For
0 . 2 な い し 5 重量％ の範囲の コ ン ド ロ イ チ ン硫酸と を含む こ と を特徴とする 易吸収性カ ル シ ウ ムを含有する食品組成物に あ る。 本願に よ る 第三の発明の特色は ゥ 二の外殻体を焼成およ び水和 さ せ る こ と に よ っ て水酸ィヒカ ル シ ウ ム と し 、 次い で こ れを有機力 ル ボ ン酸 と反応さ せて中和する こ と に よ り有機力 ル ボ ン酸のカ ル シ ゥ ム塩 と し 、 こ の カ ル シ ウ ム塩の カ ル シ ウ ム に対 して 0 . 2 な い し 5 重量％ の範囲の コ ン ド ロ ィ チ ン硫酸を添加する こ と を特徴 とす る易吸収性力 ル シ ゥ ム を含有す る食品組成物の製造方法に あ る A food composition containing easily absorbable calcium, characterized in that it contains chondroitin sulfate in the range of 0.2 to 5% by weight. The feature of the third invention according to the present application is that the outer shell is calcined and hydrated to obtain hydroxyl hydroxide, which is then converted to organic. By reacting with and neutralizing calcium carbonate, the organic calcium carbonate is converted into a calcium salt, and the calcium salt of the calcium salt is reacted with the calcium salt of the calcium salt. Adding a chondroitin sulfate in the range of 0.2 to 5% by weight to produce a food composition containing a readily absorbable ruminium. It is in
本発明の易吸収性力 ル シ ゥ ム を含有す る食品組成物は 力 ル シ ゥ ム塩のカ ル シ ウ ム分に対 して 0 . 2 ない し 5 重量％の コ ン ド ロ イ チ ン硫酸を含む こ と に よ り 生体内へのカ ル シ ウ ム の摂取が著 し く 促進 される 。 コ ン ド ロ イ チ ン硫酸は へ パ リ ン 、 ケ ラ ト 硫酸、 ヒ ア ル ロ ノ 硫酸等 と共に動物界に広 く 存在す る ス ル ホ ム コ 多糖類に属 し、 特に コ ン ド ロ イ チ ン硫酸お よびそ の塩は食品添加物 （乳化安 定剤、 魚臭除去剤） と してそ の安全性がすでに実証さ れて い る 。 コ ン ド ロ イ チ ン硫酸は コ ン ド ロ サ ミ ン誘導体に D — グル ク 口 ン 酸が； e — グ リ コ シ ド結合 した二糖類の反復結合体に硫酸がヱ ス テ ル結合 し た分子量約 5 0 0 0 0 の水溶性高分子であ っ て、 そ の水 溶液は粘稠性を呈 し、 た と えばサ メ の軟骨等か ら コ ン ド ロ イ チ ン 硫酸の c異性体と して得 られる 。  The food composition containing the easily absorbable potassium salt of the present invention contains 0.2 to 5% by weight of a chondrolyte based on the calcium content of the potassium salt. The inclusion of tin sulfate significantly accelerates the uptake of calcium into the body. Chondroitin sulfate, along with heparin, keratosulfate, hyaluronosulfate, etc., belongs to the sulfhomcopolysaccharides that exist widely in the animal kingdom, especially Roitin sulfate and its salts have already been proven safe as food additives (emulsifiers, fish odor removers). Chondroitin sulfate has D-gluconic acid in the chondrosamine derivative; and e-sulfuric acid in the repeating conjugate of disaccharide linked to glycoside. It is a water-soluble polymer having a molecular weight of about 500,000, and its aqueous solution exhibits viscous properties.For example, chondroitin sulfate is obtained from shark cartilage and the like. Obtained as the c isomer.
カ ル シ ウ ム塩に対 し て コ ン ド ロ イ チ ン硫酸等を配合する と 、 前 記の よ う に生体内への カ ル シ ウ ム の吸収性が著 し く 向上す る 。 そ の理由は必ず し も明 ら かではな いが、 ス ル ホ ム コ 多糖類は一般に 蛋白質と結合 しゃすい こ と か ら 、 腸管膜の細胞表面か ら 力 ル シ ゥ ム が C a 結合蛋白質の形態で細胞内に吸収さ れる 際に カ ル シ ゥ ム 羞替 え 用紙（規則 26) 塩の構成酸であ る乳酸等と の相互作用の影響下で カ ル シ ウ ム の吸 収を促進する もの と考え ら れる 。 When chondroitin sulfate or the like is added to the calcium salt, the absorbability of calcium into the living body is significantly improved as described above. Although the reason for this is not always clear, since sulfomucopolysaccharides generally bind proteins, Ca is bound by Ca binding from the cell surface of the intestinal membrane. Paper that is absorbed into cells in the form of proteins when it is absorbed (Rule 26) It is thought that it promotes the absorption of calcium under the influence of interaction with lactic acid, etc., which is the constituent acid of the salt.
前記カ ル シ ウ ム塩に対する コ ン ド ロ イ チ ン硫酸の配合量につ い ては、 カ ル シ ウ ム分に対 してた と えば 0 , 0 1 重量％の極めて微 量の添加ですでに カ ル シ ウ ム吸収性の向上が認め られるが、 約 6 重量％では逆にそ の吸収性が著 し く 低下する 。 コ ン ド ロ イ チ ン 硫酸は カ ル シ ウ ム分に対 して重量％で 0 . 2 %付近か ら そ の効果 が著 し く な り 、 0 . 3 〜 2 . 5 %付近で特に優れた吸収性を示す。 —方 1 %を越え る と前記効果は逆に漸減する傾向を示 し、 特に 5 %を越え る と カ ル シ ゥ ム の吸収促進効果の低下が著 し い。  Regarding the blending amount of chondroitin sulfate with respect to the above-mentioned calcium salt, an extremely small amount of, for example, 0.01% by weight based on the calcium content is added. , The absorption of calcium is already improved, but at about 6% by weight, the absorption is significantly reduced. The effect of chondroitin sulfate is remarkable from about 0.2% by weight with respect to the calcium content, and particularly from about 0.3 to 2.5% by weight. Shows excellent absorption. On the other hand, if it exceeds 1%, the above effect tends to decrease gradually, and particularly if it exceeds 5%, the effect of promoting absorption of calcium is remarkably reduced.
し たが っ て本発明においては カ ル シ ゥ ム分を基準と して約 0 . 2 〜 5 重量％ の範囲、 好ま し く は 0 . 3 ~ 2 . 5 重量％の コ ン ド ロ イ チ ン硫酸が添加さ れる 。  Therefore, in the present invention, a control range of about 0.2 to 5% by weight, preferably 0.3 to 2.5% by weight, based on the calcium content is used. Tin sulfate is added.
尚カ ル シ ウ ム は生体内への取込みの際の安全性か ら炭酸塩等の 無機塩および有機カ ル ボ ン酸塩の形態と して用い る こ とが好ま し い。 カ ル シ ウ ム源と し て は合成によ る乳酸カ ル シ ウ ム 、 ク ェ ン酸 カ ル シ ウ ム 、 炭酸カ ル シ ウ ム等 も利用で き るが、 特に天然のカ ル シゥ ム源、 た と えばゥ ニ ガ ラ 、 貝ガ ラ お よび卵殻等を焼成およ び 水和 して得 ら れる各種カ ル ボ ン酸の カ ル シ ウ ム塩が好ま し い。 本 発明 において は前記天然カ ル シ ウ ム源の中で も特に ゥ ニ外殻体を 焼成 してえ ら れる カ ル シ ウ ム が好ま しい。  In addition, calcium is preferably used as a form of an inorganic salt such as a carbonate or an organic carbonate from the viewpoint of safety during incorporation into a living body. As a calcium source, synthetic calcium lactate, calcium citrate, calcium carbonate and the like can be used. Preference is given to calcium salts of various carboxylic acids obtained by calcining and hydrating a shim source, for example, bittern, shellfish and eggshell. In the present invention, among the natural calcium sources, particularly, calcium obtained by calcining a duck shell is preferable.
ゥ 二類はそ の体壁中 に炭酸力 ル シ ゥ ム の結晶を蓄積 し こ れが石 灰質プ レ ー ト と して組合わ されて外殻体を形成 し てい る。 ゥ ニ は 主と してその卵巣部分を採取 し て食用に供さ れ、 外殻体は一部で 畑作の肥料と して利用 される他はそのま 、 投棄さ れる ので漁業廃 棄物 と し て問題を生 じ てい る。 しか し、 ゥ ニ殻は そ の大半がカ ル シ ゥ ム分であ り 、 その他比較的大量のマ グ ネ シ ウ ムや力 リ ゥ ム 、 ナ ト リ ゥ ム 、 リ ン 、 亜鉛等の微量 ミ ネ ラ ル成分を含有 したバ ラ ン ス の と れたカ ル シ ウ ム源であ る 。 ま た工業的利用の見地か ら して 差替 え 用紙（規則 26) も前記のよ う に大量の漁業廃棄物と して経済的に入手が容易であ る The second class accumulates crystals of carbonated calcium in its body wall and combines them as calcareous plates to form an outer shell. The ovary is mainly harvested for its ovary, and is used for food. And causing problems. However, most of the husk is made up of calcium and other relatively large amounts of magnesium, power rim, sodium, phosphorus, zinc, etc. It is a well-balanced calcium source containing trace mineral components. Replacement form from the point of view of industrial use (Rule 26) As mentioned above, it is economically easy to obtain as a large amount of fishery waste
本発明において用い られる ゥ ニ は棘皮動物門、 ゥ ニ網に属 し 、 食用 に供さ れ る も の と して はた と えばォ オ ノ、'フ ン ゥ 科のノ フ ン ゥ ニ ゃ ェ ゾ ノ ·？フ ン ゥ ニ 、 ナ ガ ゥ ニ科の ム ラ サ キ ゥ 二、 ラ ッ パ ゥ ニ 科の シ ラ ヒ ゲ ゥ 二等が代表的な ものであ るが、 近年北米や韓国等 海外か ら も各種の ゥ 二が大量に輸入 されてい る。  The dinosaur used in the present invention belongs to the phylum Echinoderm and the dinosaur, and is used for edible purposes, for example. Ezono ·? Representatives of Hampini, Pseudocarpaceae, and Pseudocarpaceae are representatives, but in recent years from overseas such as North America and South Korea. In addition, various types are imported in large quantities.
本発明にお いて は原料と してた と えば卵巣等を採取 した ゥ 二 の 外殻体を ま ず水洗い し適宜に乾燥す る。 次いで こ れを通常の耐熱 性の加熱炉に入れて加熱す る。 こ の場合 ゥ 二殻中の炭酸力 ル シ ゥ ム は約 9 5 0 ~ 1 1 5 0 °Cで加熱す る こ と によ り 酸化カ ル シ ウ ム と な り 、 炉体の構造に も よ るが前記温度で約 1 時間加熱す る こ と によ り原料は ほ と ん ど酸化カ ル シ ウ ム に転化されて焼成作業が完 了す る。  In the present invention, for example, the outer shell obtained by collecting ovaries and the like as a raw material is first washed with water and dried appropriately. Next, it is placed in a normal heat-resistant heating furnace and heated. In this case, the carbonated rubber in the shell becomes calcium oxide when heated at about 95 ° C to 115 ° C, and the structure of the furnace body is reduced. However, by heating at the above-mentioned temperature for about 1 hour, the raw material is almost converted into calcium oxide, and the firing operation is completed.
冷却後 こ の酸化カ ル シ ウ ム に対 して水を加えて 白色粉末状の水 酸化カ ル シ ゥ ム を生成させ、 次いで各種の酸によ つ て中和 して体 内に安全に摂取可能な カ ル シ ゥ ム塩の形態とする 。 こ の場合水酸 ィ匕カ ル シ ウ ム は炭酸カ ル シ ウ ム の よ う に中和反応時に C 0 2 を生 じな いの で水溶液中の取扱い操作が極めて容易であ る 。 水酸化力 ル シ ゥ ム に対する有機酸の量は反応後の水溶液中 に遊離の水酸化 カ ル シ ウ ムが全 く 存在 しな いよ う に化学量論的に稍過剰量で用い られる。 厳密な量は酸の種類や得 られる組成物の用途によ つ て も 異な るが反応後の水溶液の p H が約 5 〜 6 と な る よ う な量で用い られ る。  After cooling, water is added to the calcium oxide to form white powdered calcium hydroxide, which is then neutralized with various acids and safely in the body. It should be in the form of ingestible calcium salt. In this case, calcium hydroxide does not generate C02 during the neutralization reaction unlike calcium carbonate, so that handling operation in an aqueous solution is extremely easy. Hydroxidizing power The amount of organic acid relative to sodium is used in a slight excess in stoichiometry so that no free calcium hydroxide is present in the aqueous solution after the reaction. The exact amount varies depending on the type of acid and the intended use of the resulting composition, but is used in such an amount that the pH of the aqueous solution after the reaction is about 5 to 6.
中和に用い る酸と し ては摂取する際の安全性、 溶解度、 カ ル シ ゥ ム の体内への吸収性、 お よ び味や風味等の点で食品分野で一般 的に用い られてい る有機カ ルボ ン酸が用 い られ、 用途に応 じて L 一乳酸、 ク ヱ ン酸、 リ ン ゴ酸、 コ ハ ク酸、 グ ル コ ン酸、 酢酸お よ び ー ァ ス コ ル ビ ン酸等が用い られる。 差替 え 用紙 （規則 26) こ のよ う に して得 ら れた水溶液の形態 と しての配合物は次いで ス プ レ ー ド ラ ィ によ っ て粉末状又は顆粒状の形態 と さ れ用途に応 じて粉末状 も し く はタ ブ レ ッ ト 状の製品又は さ ら に水溶液 と して ド リ ン ク 剤な どと して用い られる。 造粒処理を容易にする ために 糖ア ル コ ー ル 、 特に還元麦芽糖やヱ リ ス リ ト ー ル等の賦形剤を用 いる こ と が好ま し い。 こ の形態のカ ル シ ウ ム配合物に対 して コ ン ド ロ イ チ ン硫酸がカ ル シ ウ ム分に対 して前記の範囲の割合で配合 される。 The acids used for neutralization are commonly used in the food field in terms of safety when taken, solubility, absorption of calcium into the body, and taste and flavor. Organic carboxylic acids are used, and depending on the application, L-lactate, carboxylic acid, linoleic acid, succinic acid, gluconic acid, acetic acid and acetic acid Binic acid or the like is used. Replacement form (Rule 26) The formulation in the form of an aqueous solution thus obtained is then made into a powdery or granular form by a spreader, and a powdery form depending on the application. It is used as a tablet-like product or as an aqueous solution as a linking agent. It is preferable to use excipients such as sugar alcohols, particularly reduced maltose and perisitol to facilitate the granulation process. Chondroitin sulfate is added to the calcium blend of this form at a ratio in the above range with respect to calcium.
本発明にお いて好ま し く 用い られる ウ ル殻カ ル シ ウ ム において は、 ゥ ニ外殻体を高温で焼成 し て得 られた酸化カ ル シ ウ ム を一旦 水酸化カ ル シ ウ ム に転化さ せ る ために、 その後の中和反応等の処 理が容易にな る。 ま た前記有機カ ル ボ ン酸と の中和反応に よ っ て 有機酸の カ ル シ ウ ム塩の形態と してあ る ので、 カ ル シ ウ ム を体内 に安全にかつ高い吸収率で摂取する こ と がで ぎる 。 有機酸の種類 は前記安全性およ び吸収性の他、 用途に よ り 溶解度等を考慮 して 適切に選択すればよい。  In the hull calcium which is preferably used in the present invention, calcium oxide obtained by calcining a dini outer shell at a high temperature is used to temporarily obtain calcium hydroxide. Therefore, the subsequent treatment such as a neutralization reaction is facilitated. In addition, since the organic acid is in the form of a calcium salt by the neutralization reaction with the organic carboxylic acid, the calcium can be safely and highly absorbed into the body. Can be ingested at The type of the organic acid may be appropriately selected in consideration of the solubility and the like depending on the application in addition to the above-mentioned safety and absorbability.
尚 ゥ ニ殻カ ル シ ウ ム は単品と して も他の化学合成によ る炭酸力 ル シ ゥ ム 、 卵殻カ ル シ ウ ム 、 貝殻由来の カ ル シ ウ ム に比較 して体 内への吸収性が著 し く 高い。 前記のよ う に ゥ ニ殻中においては主 成分 と し のカ ル シ ウ ム （ 5 0 %以上） の他、 特異的にマ グネ シ ゥ ム の含有量が高 く （約 2 % ) 、 こ の マ グ ネ シ ウ ム に つ いて は一般 に力 ル シ ゥ ム の生体内への吸収過程に関与す る物質であ る こ と が 知 ら れている 。 ま たそ の他に も ナ ト リ ウ ム、 カ リ ウ ム、 ィ ォ ゥ 、 リ ン 、 鉄、 亜鉛等の微量成分がバ ラ ン ス良 く 含有 されてお り 、 こ れら も ま た力 ル シ ゥ ム の体内への吸収性に寄与す る も の と考え ら れる 。 尚、 H g、 C d 、 P b、 A s 等の重金属類は約 l p p m以 下であ る か又は全 く 検出 さ れな い。  In addition, even though the husk calcium is a single product, it is in vivo compared with other chemically synthesized carbonate calcium, egg shell calcium, and shell-derived calcium. Absorbency to water is remarkably high. As described above, in the duck shell, in addition to calcium (50% or more) as the main component, the magnesium content is specifically high (about 2%). It is known that this magnesium is generally a substance that participates in the process of absorbing potassium into a living body. In addition, trace components such as sodium, potassium, zeolite, phosphorus, iron, zinc, etc. are well-balanced, and these components are also well-balanced. It is thought that it contributes to the absorption of the urine into the body. In addition, heavy metals such as Hg, Cd, Pb, and As are less than about lppm or are not detected at all.
差替 え 用紙 （規則 26) 図面の簡単な説明 Replacement form (Rule 26) BRIEF DESCRIPTION OF THE FIGURES
図 1 は本発明の各実施例によ つ て得 ら れた各種カ ル シ ゥ ム塩を 含む組成物中のカ ル シ ウ ム に対する コ ン ド ロ イ チ ン硫酸の割合を —定 （ 0 . 6 % ) に し た場合の カ ル シ ウ ム腸内吸収性 （Absorption calcium) (% ) を循環時間 （ Circulation Time) の経過 （ m i n ) と共に示す図であ る。  FIG. 1 shows the ratio of chondroitin sulfate to calcium in the compositions containing various calcium salts obtained according to the examples of the present invention. FIG. 2 is a graph showing the absorption intestinal absorption (%) of calcium in the case of 0.6%) along with the passage (min) of circulation time (Circulation Time).
図 2 は実施例 1 に よ っ て得 ら れた ゥ ニ殻由来の乳酸カ ル シ ウ ム を投与 し た場合の カ ル シ ウ ム の ラ ッ ト 腸内吸収性 （％ ) を コ ン ド ロ イ チ ン硫酸濃度を 0 . 1 5 〜 6 重量％ の範囲で変化 さ せ た場合 に つ い て時間経過 （ m i n ) と 共に示す図であ る 。 発明を実施す るための最良の形態  FIG. 2 shows the rat intestinal absorption (%) of calcium when lactate derived from husks obtained in Example 1 was administered. FIG. 4 is a diagram showing the time course (min) of the case where the concentration of droitin sulfate was changed in the range of 0.15 to 6% by weight. BEST MODE FOR CARRYING OUT THE INVENTION
以下本発明を実施例 によ つ て詳細に説明す る。  Hereinafter, the present invention will be described in detail with reference to Examples.
実施例 1 ゥ ニ殻カ ル シ ウ ム の製造方法 Example 1-Method for producing coconut shell calcium
パ フ ン ゥ 二 の卵巣を採取 した後の外殻体を水洗およ び、 自然乾 燥さ せ、 焼成炉中 において約 1 1 0 0 °Cの温度で一時間焼成 して 酸化カ ル シ ゥ ム と した後充分水和 して水酸化カ ル シ ゥ ム に転化 し た 。 こ の よ う に し て得 られた水酸ィ匕カ ル シ ウ ム 1 0 0 0 g を 1 0 リ ッ ト ル の水に溶解さ せ、 5 0 % L —乳酸約 5 0 0 0 g を加えて 7 5 °Cの温度で 1 5 分間反応さ せ て ゥ ニ殻乳酸カ ル シ ウ ム を生成 さ せた。 こ の場合乳酸は反応終了後の水溶液の p Hが約 5 ~ 6 の 範囲の所定値 と な る よ う な化学量論的に稍々 過剰な量で加え、 p H値が安定 した点で反応作業を終了 させた。 こ の水溶液に対 して 還元麦芽糖 1 5 0 g お よびコ ン ド ロ イ チ ン硫酸の 2 0 %純度組成 物約 1 5 g ( コ ン ド ロ イ チ ン硫酸 2 0 %組成物の カ ル シ ウ ム に対 する割合 ： 約 0 . 5 %、 コ ン ド ロ イ チ ン硫酸 （ 1 0 0 % ) の カ ル シ ゥ ム に対す る害 U合 ： 約 0 . 6 % ) を添加 し、 ス プ レ ー ド ラ イ ヤ —に よ っ て乾燥 してほ と ん ど白色の無臭でわずか に特有な味を有 す る水溶性の高い平均粒径 6 0 m以下の微粒子を得た。 差替 え 用紙 （規則 26) 実施例 2 After collecting the ovary of the puffer, the outer shell is washed with water and air-dried, and calcined in a firing furnace at a temperature of about 110 ° C for 1 hour to obtain calcium oxide. After being converted to water, it was sufficiently hydrated and converted to calcium hydroxide. 100 g of calcium hydroxide obtained in this manner was dissolved in 10 liters of water, and about 50% of 50% L-lactic acid was dissolved. Was added and the mixture was reacted at a temperature of 75 ° C. for 15 minutes to produce calcium coconut lactate. In this case, lactic acid was added in a stoichiometrically slightly excessive amount such that the pH of the aqueous solution after the reaction was within a predetermined range of about 5 to 6, and the pH value was stabilized. The reaction work was completed. To this aqueous solution, 150 g of reduced maltose and about 15 g of a 20% pure composition of chondroitin sulfate (capacity of a 20% chondroitin sulfate composition) The ratio of calcium to calcium: about 0.5%, and the effect of chondroitin sulfate (100%) on calcium: about 0.6%). And dried by a spreader line to obtain a nearly white, odorless, slightly watery, highly water-soluble, fine particle with an average particle size of 60 m or less. Was. Replacement form (Rule 26) Example 2
合成に よ る 炭酸カ ル シ ゥ ムお よび乳酸カ ル シ ゥ ム の水溶液に コ ン ド ロ イ チ ン硫酸を実施例 と同一の割合い と な る よ う な量で加え た他は実施例 1 と同様な手順で カ ル シ ゥ ム を含有する微粒子を製 造 し た。  The procedure was performed except that chondroitin sulfate was added to the aqueous solution of calcium carbonate and calcium lactate by the synthesis in the same proportion as in the example. Fine particles containing calcium were produced in the same procedure as in Example 1.
比較例 Comparative example
実施例 1 の製造過程で得 ら れる ゥ -殻由来の乳酸カ ル シ ゥ ム な ら びに合成によ る乳酸カ ル シ ウ ム およ び炭酸カ ノレ シ ゥ ム を夫々 実施例と 同一の割合で含み、 コ ン ド ロ イ チ ン硫酸を添加 し な い組 成物を調整 し た。  The lactate-derived calcium lactate obtained in the production process of Example 1, and the calcium lactate and canolecum carbonate obtained by the synthesis were the same as those in Example. Compositions were prepared in proportions, but without the addition of chondroitin sulfate.
実験例 1 カ ル シ ゥ ム の吸収試験 Experimental Example 1 Calcine absorption test
前記各実施例で得 ら れた カ ル シ ゥ ム塩を含む組成物を用いて、 カ ノレ シ ゥ ム に つ い て の ラ ッ ト の腸内吸収試験を行 っ た。 尚比較の ため に比較例 によ る 力 ル シ ゥ ム塩を含む組成物を対象 と して供試 した。 供試カ ル シ ウ ム塩 略号  Using the compositions containing calcium salts obtained in each of the above Examples, a rat intestinal absorption test was conducted for canoleximum. For comparison, a test was performed on the composition containing potassium salt according to the comparative example. Test calcium salt Abbreviation
炭酸カ ル シ ウ ム C a C 0 3 乳酸カ ル シ ウ ム L a C A L ゥ ニ殻乳酸カ ル シ ウ ム U C A L 乳酸カ ル シ ウ ム + コ ン ド ロ イ チ ン L a C A L 氺 炭酸カ ノレ シ ゥ ム + コ ン ド ロ イ チ ン C a C 0 3 * ゥ ニ殻乳酸カ ル シ ウ ム + コ ン ド ロ イ チ ン U C A L * 試験方法  Calcium Carbonate C a C 0 3 Calcium Lactate La CAL ゥ Coconut Lactate Calcium UCAL Calcium Lactate + Chondroitin La CAL 氺 Carbonate Noremium + chondroitin C a C 03 * ゥ Calcium lactate + chondroitin UCAL * Test method
前記各カ ル シ ウ ム塩の組成物 （ カ ル シ ウ ム換算 1 2 m g ) を含 む p H 6 . 5 の人工腸液 1 0 0 m l を調製 し、 約 8 週令 （ 2 0 0 g体重） の ラ ッ ト （ W i s t e r ： 雄） の胆汁の影響を除いた小 腸の幽門部下方 6 c m を '港流域 と して 3 7 °Cの温度で毎分 l m l 差替 え 用紙（規則 26) の港流速度に よ り 循環 さ せて力 ル シ ゥ ム を吸収さ せた。 各試供力 ル シ ゥ ム塩につ い て夫々前記ラ ッ ト 5 匹を一群と して用い、 こ れ ら ラ ッ ト に は 2 4 時間絶食 さ せた以外は副甲状腺摘出、 ビ タ ミ ン 100 ml of artificial intestinal juice having a pH of 6.5 containing each of the above-mentioned calcium salt compositions (calculated as 12 mg) was prepared for about 8 weeks (200 g). Weight (Wister: male) 6 cm below the pylorus of the small intestine, excluding the effect of bile on the bile of the small intestine, as a harbor basin at 37 ° C at a temperature of 37 ° C 26) The water was circulated at the port speed to absorb power. For each of the test ruminium salts, the above five rats were used as a group, and these rats were parathyroidectomized and vitaminized except that they were fasted for 24 hours. N
D投与等のカ ル シ ウ ム 吸収促進負荷は加えなか っ た。 カ ル シ ゥ ム  No calcium absorption promoting load such as D administration was added. Cards
の吸収率は循環液中の カ ル シ ウ ム量の減少に よ っ て各供試カ ル シ ゥ ム塩について夫々測定 し た。 結果を表 1 およ び図 1 に示す。 図  The absorption rate was measured for each of the test calcium salts by reducing the amount of calcium in the circulating fluid. The results are shown in Table 1 and Figure 1. Figure
1 中、 横軸は循環時間 （ CirculationTime ) ( m i n ) の経過を 縦軸は カ ル シ ウ ム の腸内吸収率 A B S ( % ) を夫々示す。  In Fig. 1, the abscissa indicates the progress of the circulation time (CirculationTime) (min), and the ordinate indicates the intestinal absorption rate of calcium (ABS) (%).
Circulating time min) Circulating time min)
10 20 30 40 50 60 10 20 30 40 50 60
UCAL' 3.78± 0.06 6.15 ± 0.17 6.32± 0.10 6.56± 0.05 8.36±0.10 10.16±0.20 UCAL '3.78 ± 0.06 6.15 ± 0.17 6.32 ± 0.10 6.56 ± 0.05 8.36 ± 0.10 10.16 ± 0.20
LaCAL* 4.05±1.01 3.82±0.83 4.55± 0.23 6.96± 0.38 7.82±0.46 9.05±0.53 LaCAL * 4.05 ± 1.01 3.82 ± 0.83 4.55 ± 0.23 6.96 ± 0.38 7.82 ± 0.46 9.05 ± 0.53
CaC〇3 3.06± 0.58 3.33±0.22 4.61±0.31 5.90± 0.35 6.92± 0.22 7.49±0.23 CaC〇 3 3.06 ± 0.58 3.33 ± 0.22 4.61 ± 0.31 5.90 ± 0.35 6.92 ± 0.22 7.49 ± 0.23
UCAL 2.83±0.15 3.99±0.11 4.47± 0.15 5.06±0.17 6.01± 0.30 6.58±0.17 UCAL 2.83 ± 0.15 3.99 ± 0.11 4.47 ± 0.15 5.06 ± 0.17 6.01 ± 0.30 6.58 ± 0.17
LaCAL 0.47± 0.66 2.32± 0.66 2.32± 0.66 3.25±0.69 4.19± 0.03 5.12±0.67 LaCAL 0.47 ± 0.66 2.32 ± 0.66 2.32 ± 0.66 3.25 ± 0.69 4.19 ± 0.03 5.12 ± 0.67
CaC03 1.32± 0.47 1.65± 0.47 2.64± 0.48 2.97± 0.82 3.29±0.47 4.28±0.48 CaC0 3 1.32 ± 0.47 1.65 ± 0.47 2.64 ± 0.48 2.97 ± 0.82 3.29 ± 0.47 4.28 ± 0.48
替 え 用紙 （規則 26) 表 1 および図 1 に示すよ う に 、 6 0 分港流にお け る カ ル シ ウ ム 吸収率は コ ン ド ロ イ チ ン硫酸を添加 した実施例 1 、 2 の組成物の 場合の方が無添加の比較例の組成物の場合よ り も 明 らかに高 く 、 コ ン ド ロ イ チ ン硫酸の添加によ る優れた効果を示 してい る 。 ま た これ らの中で も特に ゥ ニ殻カ ル シ ウ ム に対 して コ ン ド ロ イ チ ン硫 酸を配合 した試料が高いカ ル シ ウ ム吸収率を示 し た。 尚コ ン ド ロ ィ チ ン硫酸を添加 しな い ゥ ニ殻乳酸カ ル シ ウ ム組成物 も あ る程度 大き な吸収率が認め ら れ、 ゥ 二殻がそれ自体で も吸収性に優れた カ ル シ ウ ム源であ る こ と を示 し てい る。 その他実施例 1 におけ る 乳酸を コ ハ ク 酸に代えて得 られた組成物 も U C A L * を含む組成 物と ほ 同様な カ ル シ ウ ム吸収性を示 し た。 一方卵殻を通常の方 法で処理 して得ら れた炭酸カ ル シ ゥ ム組成物の力 ル シ ゥ ム吸収率 は U C A L * を含む組成物の約 1 5 程度であ っ た。 Replacement paper (Rule 26) As shown in Table 1 and Figure 1, the absorption rate of calcium in the 60-minute port flow was the same for the compositions of Examples 1 and 2 to which chondroitin sulfate was added. The result is clearly higher than the case of the composition of the comparative example where no additive is added, and shows the excellent effect of the addition of chondroitin sulfate. Among these, the sample containing chondroitin sulphate showed a high calcium absorption rate, especially for coconut shell calcium. In addition, chondroitin sulfate is not added. ゥ The calcium husk calcium lactate composition also has a certain large absorption rate. ゥ The shell itself is excellent in absorptivity. This indicates that it is a calcium source. In addition, the composition obtained by replacing lactic acid in Example 1 with succinic acid also showed almost the same calcium absorption as the composition containing UCAL *. On the other hand, the potassium carbonate absorption of the calcium carbonate composition obtained by processing the eggshell by the usual method was about 15 compared to the composition containing UCAL *.
実験例 2 コ ン ド ロ イ チ ン硫酸の添加量に よ る カ ル シ ウ ム吸収 率の変化 Experimental Example 2 Change in calcium absorption rate depending on the amount of chondroitin sulfate added
カ ル シ ウ ム に対する コ ン ド ロ イ チ ン硫酸 （ 1 0 0 % ) の割合を 0 . 6 〜 6 重量％ (乳酸カ ル シ ウ ム に対する コ ン ド ロ イ チ ン硫酸 2 0 %組成物の割合 0 . 5 〜 5 重量％ ) の間の 6 濃度に変化さ せ た前記実施例 1 におけ る供試化合物 U C A L * を含む組成物を用 い て実験例 1 と同様な カ ル シ ウ ム の吸収試験を行 った。 ま た コ ン ド ロ ィ チ ン硫酸の添加量の下限を確認す る ために そのカ ル シ ゥ ム に対する割合を夫々 0 . 1 5 %およ び 0 . 3 重量％ と して同様な 実験を行 っ た。 結果を表 2 およ び図 2 に示す。 図 2 中、 グ ラ フ の 縦軸はカ ル シ ウ ム吸収率 （％ ) を横軸は循環時間 （ m i n ) を示 す。  The ratio of chondroitin sulfate (100%) to calcium is 0.6 to 6% by weight (20% of chondroitin sulfate to calcium lactate) Of the test compound UCAL * in Example 1 described above in which the concentration was changed to a concentration of 0.5 to 5% by weight (0.5 to 5% by weight). Um absorption tests were performed. In order to confirm the lower limit of the amount of chondroitin sulfuric acid, a similar experiment was performed with the proportions of calcium to 0.15% and 0.3% by weight, respectively. Was performed. The results are shown in Table 2 and FIG. In Fig. 2, the vertical axis of the graph shows the calcium absorption rate (%) and the horizontal axis shows the circulation time (min).
差替 え 用紙（規則 26) 表 2 Replacement form (Rule 26) Table 2
Chondroitin Circulating time (min) Chondroitin Circulating time (min)
sulfate/Ca sulfate / Ca
cone. (¾) 10 20 30 40 50 60 cone. (¾) 10 20 30 40 50 60
0. 1 5 0.60±0.54 0.49±0.44 0.70± 0.55 0.50± 0.29 0.65± 0.22 0.64±0.28 0.15 0.60 ± 0.54 0.49 ± 0.44 0.70 ± 0.55 0.50 ± 0.29 0.65 ± 0.22 0.64 ± 0.28
0. 3 2.96± 0.89 2.22± 0.83 6.42± 2.00 6.44± 2.27 7.29±2.31 5.92±1.92 0.3 2.96 ± 0.89 2.22 ± 0.83 6.42 ± 2.00 6.44 ± 2.27 7.29 ± 2.31 5.92 ± 1.92
0. 6 3.78± 0.06 6.15± 0.17 6.32± 0.10 6.56±0.05 8.36±0.10 10.16±0.20 0.6 3.78 ± 0.06 6.15 ± 0.17 6.32 ± 0.10 6.56 ± 0.05 8.36 ± 0.10 10.16 ± 0.20
1. 2 4.68±0.64 6.54± 0.64 6.13± 0.38 5.49± 0.62 7.15±0.40 10.93±0.33 1.2 4.68 ± 0.64 6.54 ± 0.64 6.13 ± 0.38 5.49 ± 0.62 7.15 ± 0.40 10.93 ± 0.33
2. 4 3.14± 0.19 3.32±0.12 4.62±0.10 4.88± 0.16 5.79± 0.10 6.20±0.14 2.4 3.14 ± 0.19 3.32 ± 0.12 4.62 ± 0.10 4.88 ± 0.16 5.79 ± 0.10 6.20 ± 0.14
3. 6 4.56±0.23 4.31± 0.50 4.12± 0.28 5.05±0.34 4.39±0.23 4.88±0.09 3.6 4.56 ± 0.23 4.31 ± 0.50 4.12 ± 0.28 5.05 ± 0.34 4.39 ± 0.23 4.88 ± 0.09
4. 8 3.46±0.04 1.94±0.03 4.97± 0.36 5.72±0.14 5.83± 0.08 5.10±0.07 4.8 3.46 ± 0.04 1.94 ± 0.03 4.97 ± 0.36 5.72 ± 0.14 5.83 ± 0.08 5.10 ± 0.07
6. 0 3.73± 0.13 5.57± 0.17 5.37±0.17 4.52±0.06 3.98± 0.02 3.78±0.26 6.00 3.73 ± 0.13 5.57 ± 0.17 5.37 ± 0.17 4.52 ± 0.06 3.98 ± 0.02 3.78 ± 0.26
差替 え 用紙（規則 26) 前記結果か ら明 らかなよ う に、 カ ル シ ウ ム に対する コ ン ド ロ イ チ ン硫酸の割合 0 . 2 ~ 5 . 0 重量％、 特に 0 . 3 〜 2 . 5 重量 %の範囲でカ ル シ ウ ム吸収率が高 く 、 コ ン ド ロ イ チ ン硫酸の濃度 が 2 重量％か ら 5 重量％に増大する につれて吸収率が漸減 し濃度 5 重量％では その値は最大吸収濃度値の 1 %の場合に比較 して約 1 2 ま でに減少 した。 一方コ ン ド ロ イ チ ン硫酸は濃度 0 . 3 重 量％付近で も充分な C a 吸収率を示すが 0 . 1 5 重量％で は そ の 値が急激に低下 してお り約 0 . 2 重量％程度がカ ル シ ウ ム に対す る コ ン ド ロ イ チ ン硫酸の濃度の実用的な下限 と考え られる 。 Replacement form (Rule 26) As is clear from the above results, the ratio of chondroitin sulfate to calcium was in the range of 0.2 to 5.0% by weight, particularly in the range of 0.3 to 2.5% by weight. As the calcium absorption rate is high, the absorption rate gradually decreases as the concentration of chondroitin sulfate increases from 2% by weight to 5% by weight. At a concentration of 5% by weight, the value becomes the maximum absorption concentration. The value was reduced to about 12 compared to the case of 1% of the value. On the other hand, chondroitin sulfate shows a sufficient C absorptivity even at a concentration of about 0.3% by weight, but at 0.15% by weight, the value drops sharply. It is considered that about 2% by weight is a practical lower limit of the concentration of chondroitin sulfate to calcium.
尚前記各種カ ル シ ゥ ム の吸収率につ い て の実験例 1 およ び実験 例 2 において、 コ ン ド ロ イ チ ン硫酸のいずれの濃度において も港 流開始前およ び終了後の採血に よ っ て得 られた血漿中のカ ル シ ゥ ム濃度は各群間お よび港流の前後がほ と ん ど差異が認め ら れず生 体と して正常範囲にあ っ た。  In Experimental Examples 1 and 2 for the absorption rates of the various types of calcium, the concentrations of chondroitin sulfate before and after the start of port flow were observed at all concentrations of chondroitin sulfate. The concentration of calcium in the plasma obtained by the blood sampling was almost normal between the groups and before and after port flow, and was within the normal range for the organism.
実験例 3 ゥ ニ殻カ ル シ ウ ム の ラ ッ と L D 5CD試験 Experimental example 3 Lattice and LD5CD test of coconut shell calcium
本発明の実施例の組成物の出発原料の一種 と し てで用いた ゥ 二 殻カ ル シ ウ ム の急性毒性を ラ ッ ト L D 50試験によ つ て求めた。 ゥ ニ殻 の カ ル シ ウ ム C a ( O H ) 2 O 0 . 5 %溶液を 5 0 % L —乳酸 （ U — グ レー ド） で p H 5 . 0 に調製 し、 7 週令 （ 2 0 0 g体重） の ラ ッ ト （ S D雄） に対 して経口投与 （ 1 0 0 0 〜 5 0 0 0 m g / k g ) およ び静脈内投与 （ 1 0 0 〜 2 9 O m g / k g ) し、 1 4 日間にわた っ て観察 して L D 50値を求めた。  The acute toxicity of bivalve calcium used as one of the starting materials of the compositions of the examples of the present invention was determined by a rat LD50 test.ゥ Prepare a 0.5% solution of calcium (Ca (OH) 2O) in a coconut shell at pH 5.0 with 50% L-lactic acid (U-grade), and use it for 7 weeks (2 weeks). Oral (1000-500 mg / kg) and intravenous (100-29 Omg / kg) to rats (SD male) weighing ) And observed over a period of 14 days to determine the LD50 value.
観察期間中、 経口投与については各量投与群 （計 5 0 匹） につ いて実際に投与可能な 5 0 0 O m g k g の場合に 3 例の死亡を 認めたのみで他の群に は死亡例が認め ら れなかっ たので L D 50値 が算出で きず、 したが っ て L D 50を一応 5 0 0 O m g k g以上 と推定 した。 一方静脈内投与群では L D 50値は 1 8 7 . 0 m g / k g であ っ た。 以上の結果か ら本発明におけ る ゥ ニ殻カ ル シ ウ ム を含む組成物は力 ル シ ゥ ム製剤又は食品添加物等 と し て極めて安 差替 え 用紙 （規則 26) 全に用い得る も の と考え られる 。 産業上の利用可能性 During the observation period, for oral administration, only 3 deaths were observed in the case of 500 mg Omgkg that could be actually administered to each dose group (total of 50 animals), and no deaths occurred in other groups. Since no LD50 was found, the LD 50 value could not be calculated, and therefore the LD 50 was estimated to be at least 500 mg kg. On the other hand, in the intravenous group, the LD50 value was 187.0 mg / kg. From the above results, the composition containing coconut shell calcium in the present invention is extremely safe as a pharmaceutical preparation or a food additive, etc. (Rule 26) It is considered to be fully usable. Industrial applicability
前記の よ う に本発明 によ る コ ン ド ロ イ チ ン硫酸を添加 し た易吸 収性カ ル シ ゥ ムを含む組成物に よれば、 それ ら の摂取の際の生体 内へのカ ル シ ウ ム の吸収性が著 し く 促進 さ れる。 、 特に現在漁業 廃棄物と して ほ と ん ど利用価値のな い ゥ ニ殻を原料と した場合、 そ の カ ル シ ウ ム成分の体内吸収性が極めて良好な ゥ ニ殻由来の力 ル シ ゥ ム が得 られ、 こ れを配合 して得られる組成物は カ ル シ ウ ム 製剤の他、 味およ び風味にす ぐれた種々 の食品お よ び食品添加物 と し て の用途を有する 。  As described above, according to the composition containing the easily absorbable calcium to which the chondroitin sulfate according to the present invention is added, the composition into the body at the time of their ingestion can be obtained. The absorption of calcium is significantly enhanced. Particularly, it is of little value as a fishery waste at present. ゥ When husks are used as a raw material, the calcium component of the husks is extremely good in the body. A shim is obtained, and the composition obtained by blending it is used as a calcium preparation, as well as various foods and food additives that are excellent in taste and flavor. Having.
差替 え 用紙（規則 26) Replacement form (Rule 26)

Claims

請求の範囲 The scope of the claims
( 1 ) カ ル シ ウ ム塩およ び前記カ ル シ ウ ム塩の カ ル シ ウ ム分に 対 し て 0 . 2 ない し 5 重量％の範囲の コ ン ド ロ イ チ ン硫酸を含む こ と を特徴と する易吸収性カ ル シ ウ ムを含有する 食品組成物。 (1) Calcium salt and chondroitin sulfate in the range of 0.2 to 5% by weight based on the calcium content of the calcium salt. A food composition containing easily absorbable calcium, characterized in that:
( 2 ) 前記 コ ン ド ロ イ チ ン硫酸が 0 . 3 ない し 2 . 5 重量％の 範囲であ る請求項 1 記載の易吸収性カ ル シ ゥ ム を含有する食品組 成物。  (2) The food composition according to claim 1, wherein the amount of chondroitin sulfate is in the range of 0.3 to 2.5% by weight.
( 3 ) 前記カ ル シ ウ ム塩力 L 一乳酸、 ク ェ ン酸、 リ ン ゴ酸、 コ ハ ク 酸、 グル コ ン酸、 L ー ァ ス コ ル ビ ン酸およ び酢酸か ら な る群 よ り 選ばれた有機カ ルボ ン酸の塩であ る 請求項 1 記載の易吸収性 カ ル シ ゥ ム を含有する 食品組成物。  (3) The above-mentioned calcium salt power L-lactic acid, citric acid, ligonic acid, succinic acid, gluconic acid, L-ascorbic acid and acetic acid A food composition containing an easily absorbable calcium according to claim 1, which is a salt of an organic carboxylic acid selected from the group consisting of:
( 4 ) 前記カ ル シ ウ ム塩が炭酸塩であ る請求項 1 記載の易吸収 性力 ル シ ゥ ム を含有す る食品組成物。  (4) The food composition according to claim 1, wherein the calcium salt is a carbonate.
( 5 ) ゥ 二 の外殻体を処理 し て得 られる有機カ ル ボ ン酸のカ ル シ ゥ ム塩 と 、 こ の カ ル シ ウ ム 塩 の カ ル シ ウ ム分に対 して 0 . 2 な い し 2 . 5 重量％の範囲の コ ン ド ロ イ チ ン硫酸と を含む こ と を特 徵と する易吸収性カ ル シ ウ ムを含有する食品組成物。  (5) 0% for the calcium salt of organic carboxylic acid obtained by treating the outer shell and the calcium content of this calcium salt. A food composition containing easily absorbable calcium, characterized in that it contains chondroitin sulfate in the range of 2 to 2.5% by weight.
( 6 ) ゥ 二の外殻体を焼成およ び水和さ せる こ と によ っ て水 酸化カ ル シ ウ ム と し、 次いで こ れを有機カ ル ボ ン酸と反応 させて 中和する こ と に よ り有機カ ル ボ ン酸 の カ ル シ ウ ム塩と し 、 こ の 力 ル シ ゥ ム塩の カ ル シ ウ ム に対 して 0 . 2 ない し 2 . 5 重量％の範 囲の コ ン ド ロ イ チ ン硫酸を添加する こ と を特徴と する易吸収性力 ル シ ゥ ム を含有す る食品組成物の製造方法。  (6) The outer shell is calcined and hydrated to form calcium hydroxide, which is then neutralized by reaction with organic carboxylic acid As a result, the calcium salt of the organic carboxylic acid is converted to 0.2 to 2.5% by weight based on the calcium salt of the potassium salt. A method for producing a food composition containing a readily absorbable drug, which comprises adding chondroitin sulfate in the range of (1) to (4).
替 用紙（規則 26) Replacement forms (Rule 26)
PCT/JP1996/000938 1995-05-28 1996-04-05 Composition containing readily absorbable calcium and process for producing the same WO1996038058A1 (en)

Priority Applications (4)

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US08/952,738 US6203827B1 (en) 1995-05-28 1996-04-05 Composition containing readily absorbable calcium and process for producing the same
AU51625/96A AU5162596A (en) 1995-05-28 1996-04-05 Composition containing readily absorbable calcium and proces s for producing the same
DE69628754T DE69628754T2 (en) 1995-05-28 1996-04-05 EASILY ABSORBABLE CALCIUM COMPOSITION AND METHOD FOR THE PRODUCTION THEREOF
EP96908353A EP0839459B1 (en) 1995-05-28 1996-04-05 Composition containing readily absorbable calcium and process for producing the same

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JP7/153987 1995-05-28
JP15398795 1995-05-28

Publications (1)

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EP (1) EP0839459B1 (en)
KR (1) KR100394034B1 (en)
CN (1) CN1067868C (en)
AU (1) AU5162596A (en)
DE (1) DE69628754T2 (en)
WO (1) WO1996038058A1 (en)

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US20030124200A1 (en) * 1999-06-22 2003-07-03 Stone Kevin R. Cartilage enhancing food supplements with sucralose and methods of preparing the same
US7851458B2 (en) * 1999-06-22 2010-12-14 Joint Juice, Inc. Cartilage enhancing food supplements and methods of preparing the same
EP1363580B1 (en) * 2001-02-28 2007-04-11 Ezaki Glico Co., Ltd. Compositions having anti-dental caries function
US6689391B2 (en) 2001-03-30 2004-02-10 Council Of Scientific & Industrial Research Natural non-polar fluorescent dye from a non-bioluminescent marine invertebrate, compositions containing the said dye and its uses
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AU5162596A (en) 1996-12-18
US6203827B1 (en) 2001-03-20
EP0839459B1 (en) 2003-06-18
KR100394034B1 (en) 2003-11-17
CN1192124A (en) 1998-09-02
DE69628754T2 (en) 2004-04-22
DE69628754D1 (en) 2003-07-24
KR960040195A (en) 1996-12-17
EP0839459A1 (en) 1998-05-06
CN1067868C (en) 2001-07-04
EP0839459A4 (en) 1998-12-02

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